Ethers of aliphatic polyhydroxy substances



Patented Nov. 17, 1942 UNITED STATES PATENT OFFICE ETHERS OF ALIPHATICPOLYHYDROXY SUBSTANCES Benjamin R. Harris, Chicago, Ill.

.No Drawing.

1938, Serial No.

Original application August 25, 226,688, now Patent No.

2,258,892, dated October 14, 1941. Divided and this application March 5,1941, Serial No. 381,875

Claims.

Another object is the provision of processes" for producing suchmaterials.

The ethers, particularly the polyglycerol ethers, of my presentinvention meet a demand or need for certain materials having in generalsome oleaginous or fatty character and also certain othercharacteristics. These characteristics may, in general, be summed upby'the term hydrophilic property." This hydrophilic property, however,is merely a broad generalization, as in diflerent cases thecharacteristic is identiiled with the particular object or functiondesired in a particular art or industry. The ethers .of my invention,quite apart from any consideration of their structure, possess certaincharacteristics and properties as emulsiflcation agents, wetting agents,softening agents in the textile industry,

'and interface modifying substances, generally, I having valuable usesin many industries in each case imparting a property or function of adesirable character as will be in part disclosed hereinafter.

Considering the ethers of my invention more in detail such etherspossess to varying degrees aillnity for oleaginous materials as well asfor water, aqueous solutions and aqueous materials in general. Theaffinity for oleaginous materials is imparted to the ethers principallyby the presence of a lipophile group or groups, containing at least sixbut preferably from eight to eighteen or more carbon atoms, which impartto the molecule the tendency to dissolve or to disperse in oleaginousmedia; or at any rate a certain attraction for oleaginous materials. Thefree or unesterified hydroxy group or groups tend to impart to these.ethers a capacity, to varying degrees, to dissolve or disperse in wateror aqueous media in general or at least to have a certain attraction forwater and aqueous materials. On the relative potencies of the lipophileand hydrophile portions of a given molecule, the resultant activity ofthe molecule as a whole depends. These potencies are a function not onlyof the mass and number of groups constituting these relative portions ofthe molecules, but also on their structural orientation.

My ethers may at will be prepared to be pre-- dominantly lipophile orpredominantly hydrophile or balanced in the sense set out in greatdetail in U. S. Patents Nos. 1,917,250,.1,917,256, 1,917,249, and1,917,257, in which event they manifest certain unique interfacialactivities, such as the reduction of spattering of margarine duringfrying by virtue of their antispattering powers. The three arbitraryexamples indicated hereinbelow and designated respectively as A, B, and"C will help to explain one phase of the relative characteristics andbehavior of my ethers.

In this set of examples of ethers of a diglycerol, A is predominantlylipophile, C is predominantly hydrophile, and B" is intermediate and, byvirtue thereof, possesses certain interfacial modifying properties notpossessed at all by either A or "0 or not to anything like the sameextent that they are manifested by B. C is distinctly water soluble, A"is distinctly fat soluble, while B is intermediate. however, by virtueof the fact that in each of the three molecules there is present both alipophile and a hydrophile portion have marked affinities for botholeaginous and aqueous media. Insofar as interface modification inrelation to emulsification is concerned, those of my ethers which arepredominantly lipophile tend to favor the water-in-oil type of emulsion,whereas those which are predominantly hydrophile tend to favor theoil-in-water type of emulsion.

The ethers I describe herein have free hydroxy groups-at least one freehydroxy group, and, preferably, at least two per molecule-which imparthydrophilic properties to a molecule which otherwise would bepredominantly lipophile in character by virtue of the lipophile group or'perature is gradually raised to 240 degrees sired molecular magnitude.whether it be dliglycerol, triglycerol, tetraglycerol or higherpolymerized glycerols or mixtures thereof, by heating glycerol by itselfor in the presence of a catalyst,

then, if desired, reducing the content or freeing the polyglycerol orpolyglycerol mixture of unpolymerized glycerol, if any be present, andfinally etherifying the polyglycerol material, preferably, free ofglycerol, with an alcohol containing a minimum of six carbon atoms or aphenol or such alcohol or phenol mixture or with alkyl halides,sulphates or the like, or mixtures of same, by reacting the two types ofreactants with or without the presence of an etherification catalyst orcondensing agent.

These three principal steps, as well as certain other ones, in thepreparation of the polyglycerol ethersf'are described in theillustrative examples given hereinbelow.

The following examples are illustrative of the preparation ofpolyglycerols from which others of my invention may be produced:

Example"? 500 pounds of chemically pure 94% glycerol, in

which are dissolved 5 pounds of caustic soda, are heated atapproximately 260 degrees C., after initially boiling oiT the originalwaterv content, for 4 /2 hours with vigorous aspiration of CO2 over thesurface at atmospheric pressure and with continuous mechanical stirring.The carbon dioxide gas minimizes oxidation and assists in carrying oifmoisture. Finally, the product is cooled in an atmosphere of carbondioxide. The resulting polyglycerol product is a rather thick liquid ofdark amber color and moderately caramelized odor and taste, with a meanmolecular weight varyingapproximately between 148 and 163, while themolecular weight of an acyclic diglycerol is 166.

Example 2 grees C. at a pressure of 160 mm. These conditions areattained by supplying suflicient heat to reach the temperature andapplying sufficient vacuum by means of an evacuating jet or a pump, sothat, despite the supply of'nitrogen, a desired pressure of 160 mm. ofmercury is attained. As the nine hour heating period progresses, theteman approximately uniform rate and the pressure is gradually loweredto 65 mm. also at an approximately even rate, so that at the end of thenine hours the conditions are approximately 240 degrees C. at 65 mm.pressure. The temperature of the reflux condenser is adjusted to allowall moisture to escape and to cause glycerol to reflux back into thereaction mixture. The resulting polyglycerol product, when cooled toroom temperature, is very thick, almost solid, extremely dark andstrongly caramelized in odor and taste. The mean molecular weight of theproduct is 326, whereas an acyclic tetraglycerol is 314.

Example 3 300 parts of 94% chemically pure glycerol with three parts ofcaustic soda dissolved therein are heated for seven hours at atmosphericpressure at a temperature of 225 degrees to 230 degrees C., underreflux. Carbon dioxide is kept bubbling through the liquid and thereflux condenser is maintained at a temperature of about 100 degrees C.The product, when cooled. to room temperature, is a practicallyodorless, viscous syrup with a very pale straw color. Its mean molecularweight is 168.

Example 4 i even rate from the initial pressure to 70 mm.,

CO2 being continually bubbled through the mixture. Moisture, with smallproportions of other materials, continues to escape, thereby giving aproduct, which, when cooled to room temperature, is an extremely viscoussyrup of dark amber color but good odor and taste. Its mean molecularweight is 256, while the molecular weight of an acyclic triglycerol is260.

Example 5 3 parts of caustic soda are dissolved in their own weight ofwater and the solution is then mixed with 300 parts of 94% glycerol,chemically pure grade. Nitrogen" is bubbled through the mixture and heatand vacuum are applied, under reflux condenser, until the initialmoisture is driven ofi. The temperature is then raised to 250 degrees C.and heating under reflux with nitrogen bubbling through is continued fortwo and one quarter hours, manipulating the temperature fromapproximately 250 degrees to 260 degrees C., and the pressure betweenapproximately 440 mm. and 120 mm., in an upward and downward direction,respectively, as the time interval progresses, more or less as describedin the examples hereinabove. Under the herein described rate of alteringtemperature and pressure, approximately 10% of the glycerol distillsover, together with other volatile material, and apparently assists incarrying over moisture. On being allowed to cool, the product presentsthe appearance of a viscous syrup. It is practically odorless, has apale straw color and the mean C. at molecular weight is approximately1'79.

Example 6 400 parts of glycerol with 4 parts of flaked caustic soda.dissolved therein are heated under vacuo with CO2 continually bubblingthrough the mixture for two hours at a progressive pressure ofapproximately 420 mm. to approximately 49 mm. oi! mercury, and aprogressive temperature of approximately 250 degrees to 260 degrees C.(after boiling oil the initial moisture present), the temperatures andpressures being manipulated in the order described hereinabove. Oncooling to room temperature, the product is seen to be a straw colored,very viscous syrup, practically tree of all odor and taste. Its meanmolecular weight is approximately 207.

Example 7 The polyglycerol mixture obtained in Example 1 is steamdistilled at a pressure of approximately 50 mm. to mm. of mercury and ata temperature ranging from 180 degrees C. to 200 degrees C. for a periodof two hours, using approximately one part Of steam by weight to onepart of polyglycerol material. The resultant product is practicallyentirely free of caramelized odor and taste. In other respects, it hasessentially the same properties as the product of Example 1.

Still other examples of preparing polyglycerols are described in myPatents Nos. 2,022,766 and 2,023,388.

While, in the above examples, polymerization has been carried out withthe aid of caustic soda as a catalyst, polymerization may be obtainedwithout the use of catalysts, or, when catalysts are em loyed,substances other than caustic soda may be used; for example, sodiumcarbonate, sodium bicarbonate, other alkaline carbonates and hydroxides,calcium oxide, magnesium oxide, zinc oxide, trisodium phosphate, sodiumtetraborate, sodium acetate and other alkaline and potentially alkalinematerials, iodine, zinc chloride, hydrochloric acid, and the like.Furthermore, the proportion of caustic soda or other catalyst may bevaried. In general, howeve polymerization proceeds much more slowly andwith greater ditflculty without than with a catalyst. Much highertemperatures and considerably longer heating periods are required.Indeed, other things being equal, on the average it may take three tofour times as long to reach a given degree of polymerization. For thesereasons, I prefer to employ a catalyst in polymerizing the glycerol toproduce the polyglycerols which are intermediate products so far as mypresent invention is concerned.

Polyglycerols may also be prepared by purely monomeric chemicalreactions carried out on glycerol, chiorhydrins, bromhydrins,iodhydrins, allyl alcohol, diallyl ether, glycide, epichlorhydrin andthe like, as for example:

CHFO CHT OCHFCfi-CETFCICHZ- C CHz with subsequent hydrolysis VCHz-CH-CHr-O-CHz-CH-CHrO-CHz-CH-CHQOH OH OH OH OE I The partial ethersofthe polyglycerols, which are the most important products of my presentversed in the art,

may be prepared from said polyglycerols in a variety oi ways by generalmethods well known in the art for etherifying alcohols. Thus, forexample, a polvs ycerol may be reacted with an alcohol containing atleast six carbon atoms, such as hexyl alcohol, in the presence ofsulphuric acid or other condensing agents. Again, a dialykyl sulphatesuch as di-hexyl sulphate, may be reacted with a polyglycerol in thepresence of an alkali such as potassium hydroxide or sodium hydroxide.Another method which may be utilized involves adding two equivalents ofcaustic soda or the like to glycerol in which case polymerizationproceeds rapidly at lower temperatures. Then, with alkali alreadypresent, the others may be made simply by the addition of the desiredalkyl halide.

Another effective method of producing the others of the presentinvention comprises suspending a sodium or potassium or similar salt ofa polyglycerol, or other polyhydric alcohol as disclosed hereinafter, infinely divided form in an excess of a lipophile or alkyl halide andreacting the mixture at about degrees C. or higher, if necessary, withconstant agitation. After completion of the reaction, the unreactedhalide can be removed. if desired, by fractional crystallization, bydistillation, by extraction with solvents, or by any other means.Furthermore, the halide salt formed in the reaction may be eliminated inany desired manner. The reaction described makes use of the principle ofemploying one of the reactants, which is preferably liquid at thereaction temperatures utilized, as a solvent medium for carrying out thereaction. Thus, for example, a triglycerol, the hydrogen 0! two or threehydroxy groups of which is replaced, for example, by sodium orpotassium, may be suspended in a large excess of octyl bromide and thereaction effected at elevated temperatures. The sodium or potassiumbromide, as the case may be, and the unreacted octyl bromide mayinvention,

be removed from the formed ethers, if desired, in

accordance with procedures known to those In those cases where thecompounds sought to be produced are mono-ethers oi' polyglycerols or thelike, it is best to employ an excess of the polyglycerol or otherpolyhydric alcohol and only one equivalent of potassium hydroxide,sodium hydroxide, sodium or potassium, or other basic material, as thecase may be, for each equivalent of lipophile halide or higher molecularweight halide which is utilized to introduce the lipophile group intothe molecule. Thus, for example, two

mols of a diglycerol may be heated with one mol of potassium hydroxideto expel the water and the resulting potassium salt of the diglycerolmay then be reacted with one mol of alkyl halide such as lauryl chlorideto produce the monolauryl ether of diglycerol.

Tomake a poly-ether, for example, a di-ether, one equivalent of apolyglycerol or a hexahydric alcohol such as mannitol or sorbitol, orthe like, may be reacted with two equivalents of potassium hydroxide andwith at least two equivalents of lipophile halide. Or, where thelipophile halide is utilized as the solvent medium for the reaction, asdescribed hereinabove, it may be employed in considerable excess.

In the light of the above considerations, it will be clear that theamount or alkali metal or the like present in th polyhydric alcohol orcapable of replacing hydroxyl hydrogens thereof is determinative, inthis type of method of producing:

' ide are present in amounts sumcient to react with all of the alkali orthe like present.

Still other methods are illustrated in. the following equations, itbeing understood that the radical R contains at least three andpreferably from seven to seventeen carbon atoms:

It will be understood that the above represent merely illustrative modesof reactions whereby my polyglycerol ethers may be prepared. Theselection of temperatures, proportions of reactants, condensing agents,and times of reactions may be made within relatively wide limits withoutdeparting from the spirit of the invention.

The following specific examples are illustrative of methods which maying the ethers of my invention. As indicated, other methods may be used,the proportions of reacting ingredients, time of reaction, order ofsteps, and temperatures may be varied, and sup plementary processes ofpurification and the like may be resorted to wherever found desirable orconvenient. These and other variations and modifications will be evidentto those skilled in the art in the light of the guiding principles whichare disclosed herein:

Example 1 13.75 parts of 96% sodium hydroxide were dissolved in 20 partsof water and mixed with 200 parts of a polyglycerol of a mean molecularweight of 245. The mixture was heated for a period of 20 minutes at atemperature of 190 degrees C., permitting the water to escape. To thehot solution was added. with vigorous stirbe employed for preparring, asuspension of 100 parts of commercial lauryl sulfate sodium salt in 300parts of polyglycerol of a mean molecular weight of 245.

The stirring and heating'were continued for one hour at a temperature of190 degrees-220 degrees C. The reaction mixture was diluted with 3volumes of water and such an amount of hydrochloric acid added that theactual hydrochloric acid concentration amounted to 3%. The solution wasrefluxed for one hour. After cooling, a portion of the solution wasextracted with twice its volume of a 50-50 isopropyl alcoholpetroleumether mixture. The extracted aquecus layer was then extracted twice withethyl ether. The ethyl ether was evaporated off and a brown syrup wasobtained. The product obtained is a polyglycerol ether of an-l-dodecanol. This syrup was free of sulphur, indicating the absence ofthe starting material-lauryl sulfate sodium salt. The syrup wascompletely watersoluble without turbidity. The water solution was a goodfoamer and wetting agent. The syrup is a good anti-spatterer when mixedwith oleomargarine in a 1% concentration.

By the Braves test using .1% product in tap water, the skein sank in oneminute and 50 seconds. The syrup, dissolved in distilled water at aconcentration of .1%, reduced the surface tension of the distilled water57.7%. This determination was made in air at 28.5 degrees C. with a deNouy instrument.

Example 2 allowed to rise to 190 degrees C. The heating and stirringwere continued for 25 more minutes. From the reaction mixture, sodiumchloride precipitated out. The reaction product, a very viscous, strawcolored mass, is completely water soluble. 2.5 grams of the reactionmixture dissolved in 500 cc. of tap water (representing .l% of activematerial) was used for the Braves test. The skein sank in 7 minutes. The

. aqueous solution is a very good foamer. The

(ill

product obtained is a polyglycerol ether of n-loctyl alcohol.

Example 3 5.2 parts of 96% sodium hydroxide, dissolved in 10 parts ofwater, were mixed with 188 parts of polyglycerol of a mean molecularweight of 166. The mixture was heated to a temperature of 190 degrees C.while stirring and kept at that temperature for 10 minutes to drive of!water. The temperature was lowered to degrees C. While stirring, 17parts of n-l-octylchloride of 90% purity were added through a refluxcondenser. Heating was continued under reflux. with stirring for aperiod of 20 minutes, whereby the temperature of the reaction mixturegradually rose to degrees C. During this period the octylchloridegradually disappeared as was indicated by the diminishing amount ofrefluxing material. The stirring was continued for 30 more minutes at atemperature of 190 degrees- 200 degrees C. After cooling, some of thereof the above action product, a straw-colored, syrupy, viscous, clear,transparent liquid, was dissolved in water and this water solutionshowed a very fine haze only and foamed very well. The product is apolyglycerol ether of a n-l-octylalcohol.

Example 4 5.55 parts of 96% sodium hydroxide were dissolved in 10 partsof water and added to 213 parts of polyglycerol of a mean molecularweight of 245. The solution was heated to 180 degrees C. to drive of!water and 43 parts of octadecyl sulfate sodium salt were introduced. Themixture was stirred at a temperature of 190 degrees- 200 degrees for 35minutes. The reaction product was dissolved in 550 parts of water andsuch an amount of hydrochloric acid added that its ultimateconcentration amounted to 3%. The solution was kept at 100 degrees C.for one hour with occasional stirring, whereby an oily layer separated.After cooling, the oily part solidified to a half solid mass which wasremoved and redispersed in about 500 parts of water. This waterdispersion was extracted repeatedly with a 5M0 isopropyl alcohol-ethylether mixture. The solvent phase was separated and evaporated oil. Abrown solid mass was obtained which was a slight foamer in hot water andwhich, in a concentration of .1%, reduced the surface tension ofdistilled water by 29.5%, and showed a capacity for reducing thespattering of margarine during frying.

Example 5 13.75 parts of 96% sodium hydroxide were dissolved in 20 partsof water and added to 450 Parts of mannitol. The mixture was heated to190 degrees C. for a period of minutes to drive 011' water. Through areflux condenser 67 parts of 94% lauryl chloride were introduced and,with stirring, the heating was continued for four hours at a temperatureof 190 degrees- 200 degrees C. The reaction product, a dodecyl ether ofmannitol, dispersed in water with foaming.

The lipophlle group or groups of my ethers, as stated may contain as lowas six carbon atoms, but usually contain at least eight carbon atoms andordinarily from six to thirty carbons or more.

Such groups may be derived from as well'as those present in cohols suchas the sterols, as, for example, cholesterol, Isa-cholesterol,phytosterol, sitosterol, hydroaromatic alcohols, such as abietol, andsuch unsaturated alcohols as linalool, citronellol, geraniol and thelike and hydrogenated products oi the foregoing. Also included withinthe class of alcohols which may be employed are such compounds as thehydroxy and alpha-hydroxy higher aliphatic and fatty acids as, forexample, ricinoleic acid, alpha-hydroxy stearic acid, alpha-hydroxylauric acid, di-hydroxy stearlc acid, i-hydroxy-stearic acid,alpha-hydroxy palmitic acid, and the like, as well as esters of hydroxyfatty acids, such as ethyl ricinoleate, castor oil, butylalpha-hydroxystearate, cetyl hydroxystearate, and the like.

The term alcohols," as employed herein, is intended to include alcoholswhich may or may not contain other groups such as carboxylic, carbonyl,cyanogen, sulphone, sulphoxide, halogen, sulphonlc, sulphate, or otherradicals.

It is, of course, obvious that the alcohols from which the ethers may beproduced may be prepared in accordance with any desired method. Forexample, many of these alcohols may be prepared by the so-calledBouveault and Blane method or, alternatively, by the reduction or catalytie reduction with hydrogen of natural or bydrogenated animal orvegetable fats and oils, or mixtures thereof, in accordance with wellknown practices. Again the alcohols may be derived from syntheticprocesses such as by the oxidation of hydrocarbons or may be prepared bysaponification of waxes and the like. Alternatively, they may beprepared by reduction of aldehydes or by the Grignard reaction.

It is likewise apparent that mixtures of the foregoing or other alcoholsor their derivatives may be utilized in the preparation of the ethersas, for example, the mixture of alcohols resulting from thehydrogenation of coconut oil or the free fatty acids of coconut oil.Lauryl alcohol comprises about 45% of the total alcohol mixture, theremaining alcohols running from C6 to C18. Again, mixtures of alcoholssuch as are present in the so-called sperm oil alcohols,

' wool-fat, may efflcaciously be utilized. Indeed, these highermovarious sources, such as, from aliphatic straight chain and alcohol,heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecylalcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol,llnoleyl alcohol, stearyl alcohol, ricinoleyl alcohol, palmitoleylalcohol, melissyl alcohol, ceryl alcohol, carnaubyl alcohol, myricylalcohol, branched chain octyl, decyl, dodecyl, tetradecyl, hexadecyl andoctadecyl aliphatic alcohols as, for example, 2-ethyl hexanol-l, 2-nbutyl octanol-l, 2-butyl tetradecanol-l, and, in general, the highermolecular weight saturated and unsaturated aliphatic straight chain andbranched chain alcohols. Preferably, the alcohols which are utilized arethose corresponding to the fatty acids occurring in triglyceride oilsand fats of vegetable or animal origin, natural or hydrogenated, such ascorn oil, cottonseed oil, sesame oil, coconut oil, palm kernel oil,sunflower seed oil, lard, tallow. soya bean oil and the like, thosealcohols containing from 12 to 18 carbon atoms being preferred. Otheralcohols which may be employed are the oyclo-aliphatic or all-cyclicalbranched chain alcohols such as hexyl lecular weight alcohols aregenerally offered on the market in the form of mixtures of differentalcohols. If desired for any specific purpose,

. special fractions which predominate in a certain particular highermolecular weight alcohol may be utilized or, if so desired, the productsmay be prepared from a single, substantially pure alcohol.

The lipophlle group in my ethers may also comprise lipophlle radicalsderived from: phenol, cresols, xylenols, naphthols and the like, andsubstitution derivatives thereof, and sulphonated and halogenatedhydrocarbons, particularly chlorinated petroleum derivatives. Theselatter give valuable products when reacted with polyglycerol derivativesor the like, such as sodium salts thereof.

While my present invention includes the preparation of relatively puresubstances having decided advantages for certain purposes, it should berememberedthat, for many purposes, mixtures are more potent and producebetter results than the relatively pure substances. For this reason, Iprefer to use a mixture of alkyl derivatives for etheriflcation with thepolyglycerols rather than a relatively pure alkyl derivative. Mixedalkyl derivatives derived from many of the ordinary oils and fats can,therefore, be used with very good results, in many cases.

In general, my ethers, with respect to their consistency and otherpurely physical characteristics, are approximately parallel to thealcohols or mixtures of alcohols from which they are derived; that is tosay, an ether derived from a liquid alcohol is normally liquid at roomtemperature, one derived from a solid alcohol or mixture of solidalcohols is likely to be solid at room temperature. This does not mean,however, that the physical characteristics of the ethers are identicalwith those of the alcohols or phenols or the like from which they arederived. In fact, in general, the ether is somewhat softer in the caseof solid ones, and in the case of liquid ones somewhat more viscous andsyrupy than the liquid alcohols from which they are derived. The colorsof those of my ethers which are derived from polyglycerols dependlargely on the color of the polyglycerol mixture, in the sense that adark colored polyglycerol mixture will produce a dark colored ether,irrespective of how good the color of the fatty material may be. It is,therefore, advantageous in general to use polyglycerol products of goodcolor, methods for the preparation of which have been fully describedherein.

Some of the improvements in the methods I employ in accordance with mypresent applicationresult from the improved manner of preparing theinitial polyglycerols. Although various. features of the method ofpreparing the polyglycerols are new, the claims of my present inventionare directed only to the ethers and their manner of preparation.

While my invention is particularly directed to the preparation of ethersof polyglycerols which represent the most important aspect of theinvention because of their cheapness, ease of manufacture, stability,and the like, ll also include within the broader scope of my invention,

and as indicated in various of the above examples, the preparation ofethers from aliphatic polyhydroxy substances, which polyhydroxysubstances are free groups, including, for example, mannitol, sorbitol,and other hexitols or hexahydric alcohols, pentantetrol, hexylerythrite,pentite, and hexapentoles, disorbitol, dimannitol, rhamnohexite,

mannooctite, and the like, monoand di-carboxylic acid sugar or likederivatives, such as gluconic acid, mucic acid, and the like, andadditional ether-type condensation products of certain polyhydricalcohols as, for example,

onion onion CHOH (anon JHZOCHYCHTO( JH1uo-ouHcuonp-cm-o-cn-crn-o-cnflcnoun-0112011 tn.L)lhOHCllOH-CHzO-CH-(CHOll)4Cll OlI one-on onion uon onon Hr-O-CHr-CH:OCHzCH2 -}:Hz

In general, ethers prepared from aliphatic polyhydric alcoholscontaining at least six carbon atoms, which polyhydric alcohols consistonly of carbon, hydrogen, and oxygen, and wherein the oxygen-containinggroups are limited to hydroxy groups or ether groups, produce productshaving desirable properties.

from aldehyde and ketone' Br Br on on r) cua-onrcnz-ouz-cn-cno-cHHcHoHn-omon the agents of the present invention is renderedeffective, comprise natural products such as cotton, wool, linen and thelike as well as the artificially produced fibres (and fabrics), such asrayon, cellulose acetates, cellulose ethers and similar artificialproducts. It will be understood, of course, that the agents may be usedin aqueous and other media either alone or in combination with othersuitable salts of organic or inorganic character or with other interfacemodifying agents. In the dyeing and mercerising of textiles they may beemployed as effective assistants. They may be used in the leatherindustry as wetting agents in soaking, dyeing, tanning and the softeningand other treating baths for hides and skins. Their utility asemulsifying agents enables them to be employed for the preparation ofemulsions which may be used for insecticidal, fungicidal and for similaragriculture purposes. They have utility in the prepara tion of cosmeticcreams such as cold creams, vanishing creams, tissue creams, shavingcreams of the brushless and lathering type and similar cosmeticpreparations.

Another use to which the agents of my invention may be placed is for thetreatment of paper where they may be employed, for example, aspenetrating agents in the cooking of the paper pulp or the like. Theircapillary or interfacial tension reducing properties enables them to beemployed in the fruit and vegetable industry in order to effect theremoval from fruits and the like of arsenical and similar sprays. Theirinterface modifying properties also permit their use in lubricating oilsand the like enabling the production of effective boring oils, cuttingoils, drilling oils, wire drawing oils, extreme pressure lubricants andthe like. They may also be used with effect in the preparation of metaland furniture polishes, in shoe polishes, in rubber compositions, forbreaking and demulsifying petroleum emulsions such as those of thewater-in-oil. type which are encountered in oilfield operations, and forvarious other purposes I which will readily occur to those versed in theart in the light of my disclosure herein.

Examples of emulsion formulae improved by the employment of the ethersof my present invention are as follows, by way of illustration:

Cold cream Almond oil cc 1,100 White wax grams 295 Borax do 20 Di-laurylether of diglycerol ..do 40 Water cc '70 Perfume to suit.

Brushless shaving cream Stearic acid ounces 26 Mineral oil do 3 Lanolin-L do 2 Water do 64 Triethanolamine do 1 Preservative grams 5 Perfume cc5 Monocetyl ether of triglycerol "ounces" 5 The water andtriethanolamine are admixed and heated to 80 degrees C. The lanolin,stearic acid, mineral oil and preservative are then heated to 80 degreesC. and added, with constant stirring, to the aqueous solution oftriethanolamine, the stirring being continued until the mass reaches atemperature of 45 degrees C. Then the perfume, dissolved in themonocetyl ether of triglycerol, is added, with stirring, to theemulsion, and the final emulsion allowed to cool to room temperature.

Vanishing cream Stearic acid grams 400 Potassium hydroxide do 27 Watercc 1,600 Mono-hexyl ether of mannitol grams 40 Perfume to suit.

Brushless shaving cream Stearic acid grams 184 Mineral oil cc Lanolingrams 20 Water cc, =85 Glycerin cc 52 Soap (potassium stearate) grams 5Mono-lauryl ether of mannitol do (The lanolin may, if desired, beomitted without impairing the quality of the cream or its utility inshaving.)

Brushless shaving cream Grams Stearic acid Mineral oil 30 Lanolin 20Borax 5 Triethanolamine 5 Glycerine 40 Water 720 Monoor di-octyl etherof sorbitol 25 The ethers of the present invention may be employed aloneor together with lesser or greater quantities of inorganic or organiccompounds. Thus, for example, they may be employed together with saltssuch as sodium chloride, alkali metal phosphates includingpyrophosphates and tetraphosphates, sodium sulphate, alums, perboratessuch as sodium perborate, and the like. They may be utilized in thepresence of sodium carbonate, sodium bicarbonate, dilute acids such ashydrochloric, sulphurous, acetic and similar inorganic and organicacids. They may also be employed in the presence of such diversesubstances as hydrophilic gums including pectin, tragacanth, karaya,locust bean, gelatin, arabic and the like, glue, vegetable, animal, fishand mineral oils, solvents such as carbon tetrachloride, monoethyl etherof ethylene glycol, monobutyl ether of ethylene glycol, monoethyl andmonobutyl ethers of diethylene glycol, cyclohexanol, and the like. Theymay be used together with wetting, emulsifying, frothing, foaming,penetrating and detergent agents such as the higher molecular weightalcohol or alkyl sulphates, phosphates, pyrophosphates andtetraphosphates as, for example, lauryl sodium sulphate, myristyl sodiumpyrophosphate, cetyl sodium tetraphosphate, octyl sodium sulphate, oleylsodium sulphate, and the like; higher molecular weight sulphonic acidderivatives such as cetyl sodium sulphonate and lauryl sodiumsulphonate; sulphocarboxylic acid esters of higher molecular weightalcohols such as lauryl sodium sulphoacetate, dioctyl sodiumsulphosuccinate, dilauryl potassium sulpho-glutarate, laurylmonoethanolamine sulpho-acetate, and the like; sulphuric and sulphonicderivatives of condensation products of alkylolamines and higher fattyacids; Turkey-red oils; compounds of the type of isopropyl naphthalenesodium sulphonate, and other classes of wetting agents.

It will be understood that the products may be employed in the form ofimpure reaction mixtures containing substantial proportions of theeffective interface modifying agent or agents or, if desired, for anyparticular purposes, purification. procedures may be employed to producepure or substantially pure products. Those versed in the art arefamiliar with the types of purification methods which may be employedwith advantage herein, particularly in the light of the disclosures madehereinabove.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. Ethers of aliphatic polyhydroxy substances, free of ester linkages,wherein at least one hydroxyl hydrogen of the polyhydroxy substances isreplaced by an aliphatic lipophile radical of at least six carbon atoms,said ethers having at least one free hydroxy group, said aliphaticpolyhydroxy substances containing at least four hydroxy groups andconsisting of only carbon, hydrogen and oxygen and wherein theoxygencontaining groups are limited to a member of 3. Ethers ofhexahydric alcohols wherein at 5 least one hydroxyl hydrogen or thehexahydric alcohols is replaced by an-alkyl group having at least sixcarbon atoms, said ethers having at least one tree hexahydric alcohollwdroxy group.

4. Ethers in accordance with claim 3, wherein the hexahydric alcohol ismannitol.

5. Ethers in accordance with claim -3, wherein the hexahydric alcohol issorbitol.

. BENJAMIN R. HARRIS.

